WO2015146424A1 - Matériau de détection de rayonnement - Google Patents

Matériau de détection de rayonnement Download PDF

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Publication number
WO2015146424A1
WO2015146424A1 PCT/JP2015/055153 JP2015055153W WO2015146424A1 WO 2015146424 A1 WO2015146424 A1 WO 2015146424A1 JP 2015055153 W JP2015055153 W JP 2015055153W WO 2015146424 A1 WO2015146424 A1 WO 2015146424A1
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Prior art keywords
single crystal
radiation
specific resistance
gamma rays
detection material
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PCT/JP2015/055153
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English (en)
Japanese (ja)
Inventor
太郎 野島
高史 久保田
広己 高橋
優 百武
松澤　雅人
高橋　司
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三井金属鉱業株式会社
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Priority to JP2015515068A priority Critical patent/JPWO2015146424A1/ja
Publication of WO2015146424A1 publication Critical patent/WO2015146424A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/10—Inorganic compounds or compositions
    • C30B29/46—Sulfur-, selenium- or tellurium-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B13/00—Single-crystal growth by zone-melting; Refining by zone-melting
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
    • H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
    • H01L31/0264—Inorganic materials
    • H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/08—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof in which radiation controls flow of current through the device, e.g. photoresistors
    • H01L31/10—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof in which radiation controls flow of current through the device, e.g. photoresistors characterised by potential barriers, e.g. phototransistors
    • H01L31/115—Devices sensitive to very short wavelength, e.g. X-rays, gamma-rays or corpuscular radiation

Definitions

  • the present invention relates to a radiation detection material capable of detecting radiation such as alpha rays, beta rays, and gamma rays.
  • the present invention relates to a direct conversion type radiation detection material that can absorb radiation, particularly gamma rays, and convert it directly into an electrical signal.
  • a direct conversion system that converts radiation directly into electric charge and stores the charge
  • indirect conversion that converts the radiation into light once with a phosphor, and converts the light into electric charge and stores it with a photoconductive layer.
  • Non-Patent Document 1 Non-Patent Document 1
  • the material that can be represented by Tl 4 + 2x S x I 4 has a higher density than CdTe and CdZnTe, so it can not only increase the detection sensitivity of radiation, but also has a large band cap and high specific resistance. Since the energy resolution can be increased and a high-resolution image can be obtained, it is one of the remarkable radiation detection materials.
  • Tl 4 + 2x S x I 4 that has been disclosed in the past is not limited to the numerical value of specific resistance, but PET (positron emission tomography) or SPECT (single photon emission computed tomography) It was not practical for use in radiation detectors such as radiation tomography)).
  • the present invention relates to a radiation detecting material containing a single crystal body which can be represented by Tl 4 + 2x S x I 4 , it can be sufficiently used in a practical radiation detector, such as a PET, a new radiation It is intended to propose a detection material.
  • a radiation detection material having a specific resistance of 1 ⁇ 10 11 ⁇ ⁇ cm or more is proposed.
  • the radiation detection material proposed by the present invention not only absorbs radiation, particularly gamma rays, and can be directly converted into an electric signal, but also has a sufficiently high specific resistance, so that it can be used sufficiently for practical radiation detectors such as PET. Can do.
  • FIG. 3 is an X-ray diffraction profile of a single crystal produced in Example 3.
  • FIG. 4 is a transmission image (photograph) of a detection element produced using the single crystal produced in Example 3.
  • FIG. It is a wave height distribution spectrum before and after irradiating the single crystal produced in Example 3 with gamma rays from a 137 Cs ray source. Similarly, it is a wave height distribution spectrum when the single crystal body of Example 3 is irradiated with gamma rays from a 109 Cd ray source. Similarly, it is a wave height distribution spectrum when the gamma ray from a 241 Am ray source is irradiated to the single crystal body of Example 3.
  • FIG. 6 is a graph plotting the relationship between the x value of the formula: Tl 4 + 2x S x I 4 and the specific resistance of the single crystals produced in Examples 1 to 4 and Comparative Examples 1 to 3.
  • a radiation detection material containing a single crystal (referred to as “the present single crystal”).
  • the density of a single crystal that can be represented by Tl 4 + 2x S x I 4 (where x 0.77 to 1.10) is 7.25 g / cm 3 , and CdTe (6.2 g / cm 3 ) And CdZnTe (6.0 g / cm 3 ), the radiation detection sensitivity can be increased.
  • composition of this single crystal In the composition formula Tl 4 + 2x S x I 4 of this single crystal, it is important that x is 0.77 to 1.10, and among these, 0.83 or more or 1.07 or less is preferable.
  • TlI thallium iodide
  • TlI thallium iodide
  • the ampoule is made an inert gas atmosphere and the heating temperature is made as low as possible, specifically 440 to 450 ° C., while suppressing the evaporation of TlI (thallium iodide)
  • TlI thallium iodide
  • the radiation detection material of the present invention preferably has a specific resistance of 1 ⁇ 10 11 ⁇ ⁇ cm or more, more preferably 1 ⁇ 10 12 ⁇ ⁇ cm or more, and more preferably 1 ⁇ 10 13 ⁇ ⁇ cm or more. Preferably there is. Since the specific resistance of Tl 6 SI 4 that has been disclosed in the past was about 5.7 ⁇ 10 9 ⁇ ⁇ cm to 2.6 ⁇ 10 10 ⁇ ⁇ cm, the specific resistance of the radiation detection material of the present invention is higher than this. Remarkably high.
  • the single crystal body preferably has a purity of 4N or higher, more preferably 6N or higher, and particularly preferably 8N or higher.
  • the ampoule is made an inert gas atmosphere and the heating temperature is set as low as possible. Specifically, by adjusting the temperature to 440 to 450 ° C., the evaporation number of thallium iodide is suppressed and the number of purifications is performed at least 50 times or more. Then, only the high-purity tip is taken out and placed in another ampoule. It is preferable to carry out purification 50 times or more. However, it is not limited to this method.
  • the radiation detection material of the present invention is a direct conversion type radiation detection material capable of absorbing radiation, particularly gamma rays, and converting it directly into an electrical signal.
  • radiation include electromagnetic radiation such as gamma rays and X-rays, and particle radiation such as alpha rays, beta rays, electron beams, proton beams, neutron beams, and heavy particle beams.
  • the radiation detection material of the present invention can be effectively used as a radiation detection material for a radiation medical apparatus such as PET or SPECT.
  • a predetermined amount of TlI (thallium iodide) powder and a predetermined amount of Tl 2 S powder are mixed, and the mixture is sealed in a glass tube and heated to Tl.
  • a method of synthesizing a —SI compound, subjecting the resultant compound to a predetermined purification, and thereafter crystal growth to obtain a single crystal, and polishing as necessary to obtain the present single crystal can be mentioned.
  • single-phase TlI (thallium iodide) and single-phase Tl 2 S are preferably manufactured or purchased and prepared, and these are preferably used as raw materials. At this time, if either TlI (thallium iodide) or Tl 2 S has a heterogeneous phase, there is a high possibility that the produced single crystal will also have a heterogeneous phase. Like a material, it is difficult to make the specific resistance 1 ⁇ 10 11 ⁇ ⁇ cm or more.
  • the atmosphere in the sealed tube when synthesizing the Tl-SI compound is preferably an inert gas atmosphere such as argon, and the heating temperature is preferably 500 to 700 ° C, and more preferably 550 ° C or higher or 650 ° C or lower. More preferably.
  • the heating time is preferably several minutes or longer, preferably 6 hours or longer, and appropriately adjusted depending on the heating temperature.
  • the purification method is extremely important in producing this single crystal.
  • the Tl-SI compound synthesized as described above is put into an ampule, sealed as an inert atmosphere such as argon, and the ampule is heated from the surroundings with a moving heater (zone melt purification). Is preferably performed repeatedly. At this time, after performing the purification at least 50 times while suppressing the evaporation of TlI (thallium iodide) by setting the temperature during the zone purification as low as possible, specifically 440 to 450 ° C., It is preferable to take out only the high-purity tip and place it again in another ampoule, and further purify it 50 times or more.
  • TlI thallium iodide
  • evaporation of TlI thallium iodide
  • evaporation of TlI thallium iodide
  • a high-resistance single crystal can be obtained.
  • the crystal growth method is arbitrary as long as it is a method capable of growing a single crystal.
  • CZ method Czochralski method
  • HB method horizontal Bridgman method
  • VB method vertical Bridgman method
  • TH method traveling heater method
  • the polishing method is also arbitrary. For example, polishing with abrasive paper or wet polishing may be employed as appropriate.
  • the purified product thus obtained was crystal-grown by a traveling heater method (TH method) at a heating temperature of 440 ° C. and a growth rate of 5 mm / hour to obtain a single crystal, which was obtained using a 0.3 ⁇ m alumina abrasive. A single crystal was obtained by buffing.
  • TH method traveling heater method
  • FIG. 2 shows a transmission image (photograph) of the detection element produced using the single crystal produced in Example 3.
  • ⁇ Radiation evaluation: gamma-ray response measurement> The detection element was placed in an Al guard box, and the gold electrode and the external circuit were connected by a spring contact. The output of the detection element was connected to a charge sensitive preamplifier 581K type (manufactured by Clear Pulse Co., Ltd.), and the bias voltage was applied by a bias power source 6661P type (manufactured by Clear Pulse Co., Ltd.).
  • the output from the preamplifier is amplified by a spectroscopic amplifier 4417 type (manufactured by Clear Pulse Co., Ltd.), and the current peak (signal) generated by the interaction with gamma rays using a digital phosphor oscilloscope TDS5052B (manufactured by Tektronix) is used. Observed.
  • the output of the spectroscopic amplifier was processed by an analog / digital converter 1125 type (manufactured by Clear Pulse Co., Ltd.), and a signal for 600 seconds was recorded by a PC.
  • the gamma ray source 1 MBq of 137 Cs, 109 Cd, and 241 Am was used, and the gamma ray source was installed at a distance of 5 mm from the detection element.
  • the gamma-ray response was evaluated according to the following criteria, and the evaluation results are shown in Table 1.
  • ⁇ (good) A signal could be detected with gamma rays from a 137 Cs radiation source, and photoelectric peaks of gamma rays from a 109 Cd radiation source and 241 Am radiation source could be confirmed.
  • ⁇ (fair) Signals could be detected with gamma rays from a 137 Cs source, but no photopeaks of gamma rays from a 109 Cd source and 241 Am source could be confirmed.
  • X (poor) No signal was detected with gamma rays from a 137 Cs source.
  • the specific resistance of the detection element using the example 3 is as high as 1.1 ⁇ 10 13 ⁇ ⁇ cm, so the noise (dark current) at the time of gamma ray detection is low. I was able to suppress it. Similarly, in other examples, noise (dark current) at the time of gamma ray detection could be suppressed to a low level. On the other hand, since the resistance of the detection element using Comparative Example 3 is as low as 7.7 ⁇ 10 5 ⁇ ⁇ cm, noise (dark current) at the time of gamma ray detection has increased. Similarly, the noise (dark current) at the time of gamma ray detection was large for the other comparative examples.
  • FIG. 137 Cs gamma rays could be detected because the wave height distribution spectrum clearly differed with and without gamma ray irradiation.
  • FIG. 4 and FIG. 5 show the wave height distribution spectra of Example 3 when gamma rays from a 109 Cd, 241 Am radiation source are irradiated under the same conditions.
  • Example 3 has an ability to measure gamma dose by discriminating gamma ray energy.
  • Examples 2 and 4 having a large specific resistance 137 Cs gamma rays could be detected, and photoelectric peaks of 109 Cd and 241 Am ray sources were observed.
  • Example 1 gamma rays of 137 Cs could be detected, but no photoelectric peak of gamma rays from 109 Cd, 241 Am source was observed.
  • Comparative Examples 1 to 3 have low specific resistance, 137 Cs gamma rays could not be detected.
  • FIG. 8 plots the relationship between the x value of the formula: Tl 4 + 2x S x I 4 and the specific resistance for Examples 1 to 4 and Comparative Examples 1 to 3. From this figure, in order to detect gamma rays, it is necessary that the specific resistance of the radiation detection material is 10 11 ⁇ ⁇ cm or more, and x expressed in the Tl 4 + 2x S x I 4 equation at that time. Was found to be in the range of 0.77 to 1.10. Desirably, the specific resistance of the single crystal is 10 12 ⁇ ⁇ cm or more, and the range of x at that time is considered to be 0.83 or more or 1.07 or less.
  • the radiation detection material contained, in particular, the radiation detection material having a specific resistance of the single crystal of 1 ⁇ 10 11 ⁇ ⁇ cm or more can confirm ON / OFF of the 37 Cs source with respect to gamma rays.
  • the response signal of 109 Cd, 241 Am radiation source to gamma rays could be confirmed, and the photopeak could be measured. Therefore, it turned out that it can fully be used for practical radiation detectors, such as PET.

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  • Engineering & Computer Science (AREA)
  • Crystallography & Structural Chemistry (AREA)
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  • Inorganic Chemistry (AREA)
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  • Condensed Matter Physics & Semiconductors (AREA)
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Abstract

La présente invention concerne un matériau de détection de rayonnement comprenant un corps monocristallin qui peut être représenté par Tl4+2xSxI4, et concerne un matériau de détection de rayonnement qui peut être utilisé dans un détecteur de rayonnement pratique tel que PET. L'invention concerne un matériau de détection de rayonnement comprenant un corps monocristallin qui peut être représenté par la formule Tl4+2xSxI4 (où x = 0,77 à 1,10), et particulièrement, un matériau de détection de rayonnement dans lequel la résistance spécifique du corps monocristallin est de 1×1011 Ω·cm ou plus.
PCT/JP2015/055153 2014-03-24 2015-02-24 Matériau de détection de rayonnement WO2015146424A1 (fr)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004077098A1 (fr) * 2003-02-27 2004-09-10 Kabushiki Kaisha Toshiba Detecteur de rayons x et dispositif d'examen de rayons x utilisant ledit detecteur
US20120153178A1 (en) * 2010-08-10 2012-06-21 Northwestern University Methods and compositions for the detection of x-ray and gamma-ray radiation
JP2013241289A (ja) * 2012-05-18 2013-12-05 Jx Nippon Mining & Metals Corp 放射線検出素子用化合物半導体結晶、放射線検出素子、放射線検出器、および放射線検出素子用化合物半導体結晶の製造方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004077098A1 (fr) * 2003-02-27 2004-09-10 Kabushiki Kaisha Toshiba Detecteur de rayons x et dispositif d'examen de rayons x utilisant ledit detecteur
US20120153178A1 (en) * 2010-08-10 2012-06-21 Northwestern University Methods and compositions for the detection of x-ray and gamma-ray radiation
JP2013241289A (ja) * 2012-05-18 2013-12-05 Jx Nippon Mining & Metals Corp 放射線検出素子用化合物半導体結晶、放射線検出素子、放射線検出器、および放射線検出素子用化合物半導体結晶の製造方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
S. L. NGUYEN ET AL.: "Photoconductivity in Tl6 SI 4: A Novel Semiconductor for Hard Radiation Detection", CHEMISTRY OF MTERIALS, vol. 25, no. 14, 23 July 2013 (2013-07-23), pages 2868 - 2877, XP055227119, ISSN: 0897-4756 *

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